Process and System for the Addition of Promoter Metal In Situ in a Catalytic Reforming Unit

ABSTRACT

One exemplary embodiment can be a process for facilitating adding a promoter metal to at least one catalyst particle in situ in a catalytic naphtha reforming unit. The process can include introducing a compound comprising the promoter metal to the catalyst naphtha reforming unit and adding an effective amount of the promoter metal from the compound comprising the promoter metal to the catalyst particle under conditions to effect such addition and improve a conversion of a hydrocarbon feed.

FIELD OF THE INVENTION

The field of this invention generally relates to a process forconversion of hydrocarbons in a catalytic reforming unit.

DESCRIPTION OF THE RELATED ART

Numerous hydrocarbon conversion processes can be used to alter thestructure or properties of hydrocarbon streams. Generally, suchprocesses include: isomerization from straight chain paraffinic orolefinic hydrocarbons to more highly branched hydrocarbons,dehydrogenation for producing olefinic or aromatic compounds,dehydrocyclization to produce aromatics and motor fuels, alkylation toproduce commodity chemicals and motor fuels, transalkylation, andothers.

Typically such processes use catalysts to promote hydrocarbon conversionreactions. As the catalysts deactivate, it is generally desirable toregenerate them and/or add new catalyst to improve yields andprofitability.

Various catalysts and processes have been developed to converthydrocarbons. Often, such processes require periodic regeneration torecover lost catalytic activity and/or selectivity due to deactivation.Generally for fixed bed reforming units, the shutting down of theproduction unit is conducted to regenerate the catalyst whereas for amoving bed or cyclic reforming unit, the catalyst can be regeneratedwithout a unit shutdown. Eventually catalysts can be replaced due to avariety of reasons, one of which being that a new, more profitablecatalyst is available. A new catalyst may offer benefits such asincreased activity, improved selectivity, reduced deactivation, and/orextended catalyst life. It is known in the art that catalyst performancecan be improved by the inclusion of various promoters to standardcatalytic naphtha reforming catalysts that contain platinum. Thesepromoters are incorporated in the catalyst in the manufacturing of thecatalyst prior to loading the catalyst in the commercial reforming unit.Generally, one drawback of replacing an existing catalyst with a newcatalyst is the cost of replacing a large volume of catalyst, especiallyif the existing catalyst is not at its useful end of life. It would bedesirable to provide a process that permits the in situ alternation ofcatalyst by the addition of at least one promoter component to theexisting catalyst in the commercial unit to improve the performance thussaving the catalyst reload costs and minimizing the amount of processingdowntime.

SUMMARY OF THE INVENTION

One exemplary embodiment can be a process for adding a promoter metalcatalyst component in situ in a catalytic naphtha reforming unit. Theprocess can include introducing a compound comprising the promoter metalcatalyst component to the catalytic reforming process under conditionsto effect deposition of the promoter metal onto the catalyst particleand improve a conversion of a hydrocarbon feed. Selectivity of thecatalyst particle may be improved, activity of the catalyst particle maybe improved, deactivation of the catalyst particle may be reduced,undesired coking behavior of the catalyst particle may be reduced, orany combination of the above.

Another exemplary embodiment can be a process for adding a promotermetal such as indium to at least one catalyst particle in a reductionzone or a reaction zone of a reforming unit. It is generally the casethat the promoter metal such as indium will be added to a large quantityof catalyst particles such as present in a commercial catalytic naphthareforming unit, but for simplicity and ease of understanding and withoutnarrowing the scope of the invention, the invention is described hereinin terms of a catalyst particle.

A further exemplary embodiment can be a system for the in situ additionof a promoter metal to a catalyst particle in a reforming unit includinga first zone having a reducing atmosphere and a second zone having anoxidizing atmosphere. The system may include the reforming unitcontaining at least one compound comprising the promoter metal added toat least one catalyst particle. The reforming unit may be operated atconditions to facilitate the addition of an effective amount of thepromoter metal to the at least one catalyst particle for increasing theeffectiveness of the catalyst particle to catalyze reforming reactions.Therefore, a process and system disclosed herein can provide severalbenefits. Generally, a compound comprising a promoter metal is providedthat can add an effective amount of the promoter metal, such as a GroupIIIA (IUPAC 13) metal, e.g., indium; a Group IVA (IUPOAC 14) metal, e.g.tin, germanium; a rare earth metal, e.g. cerium, lanthanum, europium;and other metals such as phosphorus, nickel, iron, tungsten, molybdenum,titanium, zinc, or cadmium to a catalyst particle. Namely, the compoundcomprising the promoter metal can react so as to add the promoter metalto the catalyst particle. Such an addition can improve the performanceto generate a greater amount of the highly desired products(selectivity), increase conversion (activity), and/or decrease undesireddeactivation characteristics of the catalyst particle that initially didnot contain or had insufficient desired amounts of the promoter metal.Such an addition can also increase the level of a promoter metal of thecatalyst particle to provide further performance benefits. In oneembodiment, the compound comprising the promoter metal may be introducedto a moving bed continuous regeneration naphtha reforming process unitat the oxychlorination zone or other regeneration zones. In anotherembodiment, the compound comprising the promoter metal is introduced tothe regeneration gas of a fixed bed naphtha reforming unit during theoxychlorination step or other regeneration steps when the catalyst isbeing regenerated.

DEFINITIONS

As used herein, the term “zone” can refer to an area including one ormore equipment items and/or one or more sub-zones. Equipment items caninclude one or more reactors or reactor vessels, heaters, separators,hoppers, drums, exchangers, pipes, valves, pumps, compressors, blowers,and controllers. Additionally, an equipment item, such as a reactor orvessel, can further include one or more zones or sub-zones.

As used herein, the term “stream” can be a stream including varioushydrocarbon molecules, such as straight-chain, branched, or cyclicalkanes, alkenes, alkadienes, and alkynes, and optionally othersubstances, such as gases, e.g., hydrogen, or impurities, such as heavymetals, and sulfur and nitrogen compounds. The stream can also includearomatic and non-aromatic hydrocarbons. Moreover, the hydrocarbonmolecules may be abbreviated C1, C2, C3 . . . Cn where “n” representsthe number of carbon atoms in the hydrocarbon molecule.

As used herein, the term “metal” generally means an element that formspositive ions when its compounds are in solution.

As used herein, the term “catalytically effective amount” generallymeans an amount on a catalyst support to facilitate the reaction of atleast one compound of a hydrocarbon stream. Typically, a catalyticallyeffective amount is at least about 0.005%, preferably about 0.05%, andoptimally about 0.10%, based on the weight of the catalyst.

As used herein, the term “promotionally effective amount” generallymeans an amount on a catalyst support to increase catalytic performancein a conversion of a hydrocarbon stream to, e.g., facilitate thereaction of at least one compound in the stream. Typically, apromotionally effective amount is at least about 0.005%, preferablyabout 0.05%, and optimally about 0.10%, based on the weight of thecatalyst.

As used herein, the term “effective amount” includes amounts that canimprove the catalytic performance and/or facilitate the reaction of atleast one compound of a hydrocarbon stream.

As used herein, the term “conditions” generally means process conditionssuch as temperature, reaction time, pressure, and space velocity, andcan include an atmosphere including an oxidizing agent or a reducingagent.

As used herein, the term “oxidizing” generally refers to an environmentfacilitating a reaction of a substance with an oxidizing agent, such asoxygen.

As used herein, the term “reducing” generally refers to an environmentfacilitating a substance to gain electrons with a reducing agent, suchas hydrogen.

As used herein, the term “support” generally means a porous carriermaterial that can optionally be combined with a binder before theaddition of one or more additional catalytically active components, suchas a noble metal, or before subjecting the support to subsequentprocesses such as oxychlorination or reduction.

As used herein, the term “halogen component” generally means a halideion or any molecule that contains a halide. A halogen can includechlorine, fluorine, bromine, or iodine. As an example, a halogencomponent can include a halogen, a hydrogen halide, a halogenatedhydrocarbon, and a compound including a halogen and a metal. Typically,a halogen component is comprised in a particle and/or a catalyst.

As used herein, the term “halogen-containing compound” generally meansany molecule that contains a halide. A halogen can include chlorine,fluorine, bromine, or iodine. Typically, a halogen-containing compoundcan be part of a gas stream and include compounds such as chlorine,hydrogen chloride, or perchloroethylene, and may provide a halogencomponent to a catalyst.

As used herein, the term “particle” generally means a catalyst particlereceiving a promoter metal. The term “catalyst” can refer to catalystthat is active or has become less active or even inactive whileprocessing and converting feed, such as through the deposition of coke.

As used herein, the term “compound comprising a promoter metal”generally means a molecule or chemical species that contains at leastone promoter metal.

BRIEF DESCRIPTION OF THE DRAWINGS

The FIGURE is a schematic depiction of an exemplary catalytic naphthareforming or reforming unit.

DETAILED DESCRIPTION

The in situ addition of an effective amount of a promoter metal canoccur in units having fixed or moving beds. Preferably, the unit has amoving bed with continuous catalyst regeneration. Generally, at leastone compound comprising a promoter metal is provided to an existingcatalyst bed of at least one catalyst particle in a commercial reformingunit. Typically, the existing catalyst is a commercially manufacturedcatalyst that has been loaded in the reactor vessels and is ready tofacilitate the conversion of a naphtha feed or is already in the processof converting feed. In addition, the existing catalyst can also be inthe process of regeneration which is periodically needed to restore thecatalyst activity as described below. The addition of the compound withthe promoter metal can improve the performance (i.e., the activity,selectivity, and/or deactivation characteristics) of the catalystparticle that initially does not contain or may contain less thandesired amounts of the metal promoter. Additionally, such an additioncan also increase the level of a metal promoter of the catalyst particleto provide further performance benefits.

Referring to the FIGURE, an exemplary catalytic naphtha reforming unit100 can include a first zone 200 including a reducing atmosphere and asecond zone 300, which can be a regeneration zone, including anoxidizing atmosphere. Lifts 120 and 124 can transfer the catalystparticles, generally in the form of pills, spheres, and/or extrudates,between the zones 200 and 300. Also depicted are several access points390, which are discussed hereinafter. Such a unit 100 can providecontinuous catalyst regeneration and exemplary units are disclosed in,for example, U.S. Pat. No. 5,958,216; U.S. Pat. No. 6,034,018; and US2006/0013763 A1. The unit 100 can have portions operated at the same ordifferent pressures, which can be atmospheric or greater. In oneexemplary embodiment, a system 110 for the in situ addition of apromoter metal can be associated with the unit 100 and is furtherdiscussed below.

Typically, a hydrocarbon feed 205 and a hydrogen-containing stream 210is combined in stream 220, heated, and then may be received in the firstzone 200 that can include a reduction zone 240 and a reaction zone 280.Usually, the operating temperature in the first zone 200 is about 100 toabout 600° C., preferably about 350 to about 600° C., and optimallyabout 500 to about 600° C. The pressure can be in the range of about 100kPa absolute to about 1700 kPa absolute. The first zone 200 can includethe combined hydrocarbon and hydrogen stream 220, with at least oneparticle or catalyst as described further below and a halogen componentsuch as compound containing a fluoride or a chloride, preferably achloride. Typically, the concentration of hydrogen in 210 is at leastabout 15%, preferably at least about 50%, by mole. Usually, thehydrocarbon feed 205 for catalytic reforming is a petroleum fractionknown as naphtha having an initial boiling point of about 82° C. and anend boiling point of about 204° C. The catalytic reforming process isparticularly applicable to the treatment of straight run naphtha feedsas well as processed naphthas comprised of relatively largeconcentrations of naphthenic and paraffinic hydrocarbons.

Generally, the regenerated catalyst (described in further detailhereinafter) enters the reduction zone 240 of the first zone 200 fromthe lift 120. The reduction zone 240 can include one or more sub-zonesand/or reduction vessels and typically includes a reducing gas, such ashydrogen, to reduce one or more metal components present on theregenerated catalyst. The reducing gas can be provided via a line 250.Typically, a concentration of hydrogen in a gas is at least about 15%,preferably at least about 50%, and optimally at least about 75%, bymole, with the balance optionally being C1 to C6 hydrocarbons. In somepreferred embodiments, a concentration of hydrogen in a gas can be about60 to about 99.9%, by mole. The temperature can be about 120 to about570° C., preferably about 200 to about 550° C., at a pressure of about450 to about 1500 kPa absolute. A mole ratio of halide:H₂O, desirablyCl⁻:H₂O, is about 0.2:1 to about 0.6:1.

Afterwards, the regenerated catalyst can pass to the reaction zone 280.The combined hydrogen and hydrocarbon feed stream 220 can be introducedto zone 280. The reaction zone 280 can include one or more sub-zonesand/or reaction vessels with heaters between sub-zones or reactors forconducting reforming reactions. Reforming may be defined as the totaleffect produced by dehydrogenation of cyclohexanes anddehydroisomerization of alkylcyclopentanes to yield aromatics,dehydrogenation of paraffins to yield olefins, dehydrocyclization ofparaffins and olefins to yield aromatics, isomerization of n-paraffins,isomerization of alkylcycloparaffins to yield cyclohexanes,isomerization of substituted aromatics, hydrocracking of paraffins, anddealkylation of aromatics. Preferably, the reaction zone 280 includes amoving catalyst bed that can be countercurrent, cocurrent, crosscurrent,or a combination thereof, and the catalyst bed can be any suitableshape, such as rectangular, annular or spherical. The reaction zone 280can be at a temperature of about 450 to about 550° C., a pressure ofabout 270 kPa absolute to about 1500 kPa absolute, a hydrogen tohydrocarbon mole ratio from about 1 to about 5, and a liquid hourlyspace velocity of about 0.5 to about 4 hour⁻¹. In some preferredembodiments, a concentration of hydrogen in a gas can be about 55 toabout 65%, by mole. After the reforming reaction, the hydrocarbon streamcan be sent for further processing and the catalyst can be passed to thelift 124 for regeneration.

The spent catalyst can exit the lift 124 into the regeneration zone 300.Typically, the catalyst fines are separated and removed before going tothe regeneration zone 300. Generally, a temperature is about 40 to about600° C. and a pressure is about 100 kPa absolute to about 520 kPaabsolute. Most of the regeneration zone 300 can operate from about 350to about 700° C. The regeneration zone 300 can include an incoming gasstream that has a halogen-containing compound in at least one sub-zone.

The regeneration zone 300 can include an oxidation zone 320, aredispersion zone 340, a drying zone 360, and a cooling zone 380. Notethat the term “zone” can refer to an area including one or moreequipment items and/or one or more sub-zones. Equipment items caninclude one or more vessels, heaters, separators, hoppers, drums,exchangers, pipes, pumps, compressors, blowers, valves, and controllers.Additionally, an equipment item can further include one or more zones orsub-zones. Also, in a fixed bed mode, the regeneration zone may includeat least a coke burn step, a proof burn step and an oxychlorinationstep. In the moving bed embodiment of the FIGURE, the oxidation zone 320can include an oxidizing atmosphere of about 0.5% to about 1.5%, byvolume, oxygen. In some instances, the atmosphere may contain more thanabout 1.5%, by volume, oxygen. Typically, spent catalyst is contactedwith the oxidizing atmosphere to remove accumulated coke on the catalystsurfaces. Moreover, chloride on the catalyst may also be stripped.Within the zone 320, coke is usually oxidized at a gas temperature ofabout 450 to about 600° C. The pressure can be at atmospheric pressureor greater. The catalyst can be preheated prior to leaving the oxidationzone via the hot outlet gases from the oxidation zone.

After exiting the oxidation zone 320, the catalyst particles can pass tothe redispersion zone 340. In the redispersion zone 340, a gas isprovided having a halogen-containing compound, such as a chloridecompound for redispersing the catalyst metal. Generally, theredispersion gas also contains either chlorine or another chloro-speciesthat can be converted to chlorine. Typically, the chlorine orchloro-species is introduced in a small stream of carrier gas added tothe redispersion gas. Generally, the redispersion is effected at a gastemperature of about 425 to about 600° C., preferably about 510 to about540° C. Typically, a concentration of chlorine of about 0.01 to 0.2 molepercent of the gas and in the presence of oxygen is used to promoteredispersion. A halide:H₂O, preferably Cl⁻:H₂O, mole ratio can be about0.07:1 to about 16:1, preferably about 0.07:1 to about 3.2:1.

The catalyst particles can pass to the drying zone 360 after passingthrough the redispersion zone 340. Typically, the catalyst particles aredried with air heated up to about 600° C., preferably up to about 538°C. Afterwards, the catalyst particles can be passed to the cooling zone380 at a temperature of about 40 to about 260° C. before passing throughvarious other subzones and then through a lock hopper to the lift 124 torepeat in a continuous manner.

Referring to the FIGURE, the catalyst and the combined hydrogen andhydrocarbon feed stream 220 can pass through the first zone 200, and thecatalyst can be regenerated in the second zone 300. One exemplaryapplication is the introduction of a compound comprising the promotermetal to the catalytic reforming process such as to add a promoter metalin situ to a catalyst particle. The compound comprising the promotermetal can be added anywhere to the unit 100, but preferably it is addedto the first zone 200 including a reducing atmosphere, or the secondzone 300 including an oxidizing atmosphere. The compound comprising thepromoter metal can also be added simultaneously to both zones 200 and300. Furthermore, several different compounds, each with the same or adifferent promoter metal can be added in multiple combinations to zones200 and 300 at multiple locations.

If the compound comprising the promoter metal is added to the first zone200, preferably the compound comprising the promoter metal is added tothe naphtha feed stream 205, and/or to the hydrogen-containing gasstream 210, and/or to the combined hydrogen/naphtha feed stream 220and/or the reduction zone 240, and/or the reaction zone 280 through theone or more access points 390. Alternatively, the compound comprisingthe promoter metal can be added to the regeneration zone 300, preferablyat the oxidation zone 320, and/or the redispersion zone 340, and/or thedrying zone 360, and/or the cooling zone 380 through one or more accesspoints 390. In one embodiment, a solution of HCl, water and indiumchloride may be provided to facilitate the addition of indium to zone300. Furthermore, the compound comprising the promoter metal can beadded at lifts 120 and/or 124 at the access points 390.

The system 110 disclosed herein can provide at least one catalystparticle in the reforming unit 100. The at least one catalyst particlecan be one or more catalyst particles circulating through the unit 100,as described above. Each catalyst particle can include a support and oneor more additional components that can be incorporated in the supportduring, or after, the formation of the support. Generally, the supportcan be formed by an oil-drop method or extruded, although other methodscan be utilized. The support can include a porous carrier material, suchas a refractory inorganic oxide or a molecular sieve, and a binder in aweight ratio of about 1:99 to about 99:1, preferably about 10:90 toabout 90:10. The carrier material can include:

-   -   (1) a refractory inorganic oxide such as an alumina, a magnesia,        a titania, a zirconia, a chromia, a zinc oxide, a thoria, a        boria, a silica-alumina, a silica-magnesia, a chromia-alumina,        an alumina-boria, or a silica-zirconia;    -   (2) a ceramic, a porcelain, or a bauxite;    -   (3) a silica or a silica gel, a silicon carbide, a clay or a        silicate synthetically prepared or naturally occurring, which        may or may not be acid treated, for example an attapulgus clay,        a diatomaceous earth, a fuller's earth, a kaolin, or a        kieselguhr;    -   (4) a crystalline zeolitic aluminosilicate, such as an        X-zeolite, an Y-zeolite, a mordenite, a β-zeolite, a Ω-zeolite        or an L-zeolite, either in the hydrogen form or most preferably        in nonacidic form with one or more alkali metals occupying the        cationic exchangeable sites;    -   (5) a non-zeolitic molecular sieve, such as an aluminophosphate        or a silico-alumino-phosphate; or    -   (6) a combination of one or more materials from one or more of        these groups.        In one preferred embodiment, the porous carrier is an alumina,        such as a gamma alumina.

The binder can include an alumina, a magnesia, a zirconia, a chromia, atitania, a boria, a thoria, a phosphate, a zinc oxide, a silica, or amixture thereof.

The catalyst particle may contain one or more other components addedduring the formation of the support and/or incorporated afterwards.These components can be one or more metals or non-metals and include:(1) a Group VIII (IUPAC 8, 9 and 10) element, (2) a Group IIIA (IUAC 13)element, (3) a Group IVA (IUPAC 14) element, and (4) a halogencomponent.

Preferably, the Group VIII element is platinum and the catalyst particlecontains a catalytically effective amount of platinum. Typically, thecatalyst contains about 0.01 to about 2%, by weight, of the Group VIIIelement, preferably platinum, based on the weight of the catalyst. Themetal components may be incorporated in the support in any suitablemanner, such as coprecipitation, ion-exchange or impregnation. Apreferred method of preparing the catalyst can involve impregnating aporous carrier material with a soluble, decomposable group VIIIcompound. As an example, the platinum metal may be added by comminglingthe support with an aqueous solution of chloroplatinic, chloroiridic orchloropalladic acid. Other water-soluble compounds or complexes of groupVIII metals may be employed in impregnating solutions and includeplatinum nitrate, platinum sulfite acid, ammonium chloroplatinate,bromoplatinic acid, platinum trichloride, platinum tetrachloridehydrate, platinum dichlorocarbonyl dichloride, dinitrodiaminoplatinum,sodium tetranitroplatinate (II), palladium chloride, palladium nitrate,palladium sulfate, diamminepalladium (II) hydroxide,tetraamminepalladium (II) chloride, hexa-amminerhodium chloride, rhodiumcarbonylchloride, rhodium trichloride hydrate, rhodium nitrate, sodiumhexachlororhodate (III), sodium hexanitrorhodate (III), iridiumtribromide, iridium dichloride, iridium tetrachloride, sodiumhexanitroiridate (III), potassium or sodium chloroiridate, or potassiumrhodium oxalate. Use of these compounds may also provide at least partof the halogen component, particularly by adding an acid, such ashydrogen chloride. In addition, the impregnation can occur aftercalcination of the support.

Similarly, the catalyst particle can contain a group IIIA metalincorporated in the support in any suitable manner, such ascoprecipitation, ion-exchange or impregnation. A preferred method ofpreparing the catalyst can involve impregnating a porous carriermaterial with a soluble, decomposable group IIIA compound. As anexample, an indium metal may be added by an impregnating aqueoussolution of indium chloride (InCl₃) or indium nitrate (In(NO₃)₃) andhydrochloric acid. Use of these compounds may also provide at least partof the halogen component. Other solution modifiers which may be usedinclude nitric acid and ammonia hydroxide.

Typically, the catalyst particle contains zero up to no more than about1%, by weight, of the Group IIIA element, preferably indium, based onthe weight of the catalyst. The indium can be present as a metal on thecatalyst or as one or more compounds or species, such as, but notlimited to, indium oxide, a mixture of platinum, tin and indium, orindium chloride.

The catalyst particle can contain another promoter from Group IVA and/orother elements. A preferable group IVA element is tin, germanium, orlead, more preferably tin. Yet another promoter that optionally can beincluded is rhenium; a rare earth metal, such as cerium, lanthanum,and/or europium; phosphorus; nickel; iron; tungsten; molybdenum;titanium; zinc; or cadmium. Also, the catalyst can contain a combinationof these elements. Generally, the catalyst contains about 0.01 to about5%, by weight, based on the weight of the catalyst. Optionally, thecatalyst may also contain one or more group IA and IIA metals (alkaliand alkaline-earth metals) in about 0.01 to about 5%, by weight, basedon the weight of the catalyst.

In the manufacture of the catalyst particle, the promoter, such as agroup IVA metal, may be incorporated in the catalyst in any suitablemanner to achieve a homogeneous dispersion, such as by coprecipitationwith the porous carrier material, ion-exchange with the carriermaterial, or impregnation of the carrier material at any stage in thepreparation. One method of incorporating the group IVA metal componentinto the catalyst composite involves the utilization of a soluble,decomposable compound of a group IVA metal to impregnate and dispersethe metal throughout the porous carrier material. The group IVA metalcomponent may be impregnated either prior to, simultaneously with, orafter the other components are added to the carrier material. Thus, thegroup IVA metal component may be added to the carrier material bycommingling the carrier material with an aqueous solution of a suitablemetal salt or soluble compound such as stannous bromide, stannouschloride, stannic chloride, or stannic chloride pentahydrate; orgermanium oxide, germanium tetraethoxide, or germanium tetrachloride; orlead nitrate, lead acetate, or lead chlorate. The utilization of metalchloride compounds may also provide at least part of the halogencomponent. In one preferred embodiment, at least one organic metalcompound such as trimethyltin chloride and/or dimethyltin dichloride areincorporated into the catalyst during the peptization of the inorganicoxide binder, preferably during peptization of alumina with hydrogenchloride or nitric acid.

The catalyst particle can also contain a halogen component and can befluorine, chlorine, bromine, iodine, astatine or a combination thereof.Preferably the halogen component is chlorine. The catalyst particle cancontain typically about 0.1 to about 10%, preferably about 0.5 to about2.0%, and optimally about 0.7 to about 1.3%, by weight, of the halogencomponent, preferably chlorine, based on the weight of the catalyst. Thehalogen component can be added with one or more of the metals and/or oneor more promoters. Furthermore, the halogen component can be adjusted byemploying a halogen-containing compound, such as chlorine or hydrogenchloride, in air or an oxygen atmosphere at a temperature of about 370to about 600° C. Water may be present during the contacting step inorder to aid in the adjustment.

For the catalyst particle, the components can be impregnated together,e.g., co-impregnated, or separately with one or more optionalcalcination steps there between. The catalyst particles or catalysts canbe made to methods known to those skilled in the art, as disclosed in US2006/0102520 A1 and/or U.S. Pat. No. 5,883,032. The supports can beformed into spheres or extrudates optionally with one or morecomponents.

The amount of material contained by the catalyst particles can bemeasured by methods known to those of skill in the art. As an example,UOP method 274-94 can be used for platinum and other group VIII metals,UOP method 303-87 can be used for tin and other group IVA metals, andUOP method 873-86 can be used for noble metals and modifiers,particularly indium, in catalysts by inductively coupled plasma atomicemission spectroscopy. The halogen component, particularly chloride, canbe determined by UOP method 979-02 by x-ray fluorescence or by UOPmethod 291-02 by potentiometric titration.

One class of suitable compounds that contain a promoter metal are thosethat are soluble in a hydrocarbon naphtha feed. These types of compoundscan consist of organometallic compounds, i.e. compounds that contain acarbon-metal linkage including, but limited to, tetrabutyltin,tetrabutylgermanium, tetraethyl lead, tetraethylgermanium,tetraethyltin, triphenylindium, and tetrapropylgermanium. Another classof suitable compounds that contain a promoter metal are those that canbe made into a solution with water or water and an acid. The compoundscan include halides, nitrates, acetates, tartrates, citrates,carbonates, rhenates, tungstates, and molybdates. The preferredcompounds are halides and more preferred are chlorides such as, but notlimited to, indium chloride, tin chloride, germanium chloride, ceriumchloride, lanthanum chloride, lead chloride, and europium chloride. Thechloride compounds are specifically advantageous since these can alsoadd to the chloride component of the catalyst and not introducepotential undesired impurities. Other compound classes with promotermetals may also be used.

Generally, from the compound comprising the promoter metal, acatalytically effective amount is added to the catalyst particle.Typically, at least about 0.005%, preferably at least about 0.05%, andoptimally at least about 0.1%, by weight, of the Group IIIA element,Group IVA element, rare earth metal element, or other element such asphosphorus, nickel, iron, tungsten, molybdenum, titanium, zinc, orcadmium is added to the catalyst particle, based on the weight of thecatalyst particle.

Generally, for the addition of the compound with the promoter metal, asolution of the compound is made, added to a holding tank and thenpumped to zones 200 and 300 typically at addition points 390. The pipeor lines can be heated to aid in the transfer of the compound to zones200 and 300. Optionally, an inert carrier gas such as nitrogen can beadded to the line to aid in the transfer of the compound to zones 200and 300. The content of the solution depends on the class of compoundused. For the class of compounds that are soluble in water and/or waterand inorganic acids such as HCl, a solution is made with water, acid andthe compound that contains the promoter metal. For organometalliccompounds that contain the promoter metal, a solution of theorganometallic compound can be made with a small portion of the naphthafeed or other organic solvent with 6 to 12 carbons which can include forexample benzene, toluene, n-hexane, n-heptane, methylcyclohexene, andmixtures thereof. The preferred locations for the addition of theorganometallic compounds are to streams 205, 210, 220 and zone 280. Ingeneral, for all compounds added to zones 200 and 300, the compound willvolatilize under reforming conditions, adsorb onto the catalyst and/ordecompose and/or react leaving a deposited promoter metal species on thecatalyst.

The following example is intended to further illustrate the invention.This embodiment and demonstration of the invention is not meant to limitthe claims of this invention to the particular details of the example.

EXAMPLE

200 cc of a fresh commercial continuous regeneration catalyst comprisingPt, Sn, and Cl on gamma alumina was loaded into a quartz reactor in fourbeds containing 50 cc each of the catalyst. The beds were numberedsequentially with Bed 5 located nearest to the top of the reactor, andbed 2 located nearest to the bottom of the reactor. The beds wereseparated by quartz wool. At the bottom of the reactor, in bed 1, a bedof 200 cc of the gamma alumina support was loaded. The initial indiumlevels of the catalyst and of the support were zero wt. %. Spacers werelocated above the top bed.

A regeneration procedure was conducted in the reactor. The steps of theregeneration procedure included (1) a heat up period in air ramping thetemperature from ambient to 510° C. at 1.4° C./min. (2) introduction ofCl2 and a HCl-containing solution as described below, during anoxychlorination step for 8 hours at 510° C. (3) Cool down period withfull air to reach 93° C. (4) a reheat/ramp period using 15 mol %hydrogen stream ramping from 93° C. to 566° C. at 1.5° C./min. (5) areduction step for 2 hours at 566° C. and (6) a final cool down periodto 93° C. in 15 mol % hydrogen.

100 cc of a solution of HCl, InCl₃, and water was prepared by mixing2.67 g InCl₃, 15.35 g HCl solution (36.5 wt % HCl), and 87.16 g water.The solution was flowed to the reactor via a pump. A total of 48.65 ccof the solution was injected, continuously, over the 8 houroxychlorination step. Inside the reactor, the solution dripped onto thespacers above Bed 5. The solution volatized and was swept to thecatalyst by the air stream that entered through a second reactor inletline.

Upon completion of the regeneration process, each catalyst bed wasunloaded keeping each bed separate and analyzed by inductively coupledplasma atomic emission spectroscopy using UOP Method 873-86. Bed 5contained 0.502 wt. % indium, bed 4 contained 0.011 wt. % indium, bed 3contained 0.008 wt. % indium, bed 2 contained less than 0.001 wt %indium, and bed 1 contained less than 0.001 wt % indium. A significantamount of Indium was added to the top catalyst bed, bed 5, with smalleramounts on beds 3 and 4. This experiment demonstrated that a compoundcomprising indium can be introduced into a regeneration system withindium successfully being added to a finished catalyst in the system. Ina moving bed application, the catalyst particles in the bed physicallyclosest to the location of introduction of the indium periodic additionof the compound comprising indium may receive the bulk of the indiumaddition, but since the particles move through the regeneration system,and the indium may be periodically added, with time the indium can beadded over the inventory of catalyst.

1. A process for adding at least one promoter metal to a catalystparticle in situ in a catalytic naphtha reforming unit comprisingintroducing a compound comprising the promoter metal into the catalyticnaphtha reforming unit under conditions effective to add the promotermetal to a catalyst particle including a temperature of less than 600°C. and wherein the promoter metal is effective for increasing theselectivity or the activity of the catalyst particle or decreasing thedeactivation of the catalyst particle for naphtha reforming reactions.2. The process of claim 1, wherein the catalytic naphtha reforming unitis a moving bed continuous regeneration unit and the compound comprisingthe promoter metal is introduced to a zone selected from the groupconsisting of the oxidation zone, the redispersion zone, the dryingzone, the cooling zone, or a combination thereof of the moving bedcontinuous regeneration unit.
 3. The process of claim 2 wherein the zoneis operated at a temperature from about 40 to about 600° C. and apressure from about 100 kPa absolute to about 520 kPa absolute.
 4. Theprocess of claim 1, wherein the catalytic naphtha reforming unit is afixed bed unit and the compound comprising the promoter metal isintroduced to the regeneration gas during a step selected from the groupconsisting of the coke burn step, the proof burn step, theoxychlorination step, or a combination thereof when the catalyst isbeing regenerated.
 5. The process of claim 4 wherein the step conductedat a temperature from about 40 to about 700° C. and a pressure fromabout 100 kPa absolute to about 520 kPa absolute.
 6. The process ofclaim 1, wherein the compound comprising the promoter metal isintroduced to a naphtha feed stream entering the catalytic naphthareforming unit.
 7. The process according to claim 1, wherein thepromoter metal is selected from the group consisting of Group IIIA(IUPAC 13) elements, Group IVA (IUPAC 14) elements, and rare earthelements.
 8. The process of claim 1 wherein the promoter metal isselected from the group consisting of In, Sn, Ga, Ge, Ce, Th, Ho, Er,Tm, Yb, Lu, La and Eu.
 9. The process of claim 1 wherein the promotermetal in indium.
 10. The process of claim 1 wherein the compoundcomprising the promoter metal is in solution.
 11. The process accordingto claim 1, wherein the promoter metal comprises indium, the catalystparticle comprises no more than about 1.0%, by weight, of indium, basedon the weight of the catalyst particle before the adding of at least onepromoter metal to the catalyst particle in situ.
 12. The process ofclaim 1 wherein the catalyst particle comprises a support and at leastone catalytic metal deposited on the support.
 13. The process accordingto claim 1, wherein the reforming unit comprises: a reduction zone; areaction zone; and a regeneration zone comprising: an oxidation zone, aredispersion zone, a drying zone, and a cooling zone; and wherein theprocess further comprises adding the compound comprising the promotermetal to at least one of the reduction zone, the reaction zone and theregeneration zone.
 14. The process according to claim 13, wherein thecompound comprising the promoter metal is introduced to the reductionzone or the reaction zone and the addition of the promoter metal to thecatalyst particle occurs in a reducing atmosphere comprising hydrogen.15. The process according to claim 1, wherein the compound comprisingthe promoter metal is introduced to the catalytic naphtha refining unitas a co-feed with a halogen containing compound and water.
 16. Theprocess according to claim 13, wherein compound comprising the promotermetal is added to the regeneration zone and the addition of the promotermetal to the catalyst particle occurs in an oxidizing atmospherecomprising oxygen.
 17. A system for the in situ addition of a promotermetal in a reforming unit comprising a first zone comprising a reducingatmosphere, and a second zone comprising an oxidizing atmosphere, thesystem comprising the reforming unit containing at least one compoundcomprising the promoter metal added to at least one catalyst particleand operating at conditions to facilitate addition of an effectiveamount of the promoter metal to the at least one catalyst particle forincreasing the selectivity or activity of the catalyst particle ordecreasing the deactivation of the catalyst particle.
 18. The systemaccording to claim 17, wherein the metal catalyst component comprisesindium.